WO2016024305A1 - 塗装金属板、その製造方法および外装建材 - Google Patents

塗装金属板、その製造方法および外装建材 Download PDF

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Publication number
WO2016024305A1
WO2016024305A1 PCT/JP2014/006272 JP2014006272W WO2016024305A1 WO 2016024305 A1 WO2016024305 A1 WO 2016024305A1 JP 2014006272 W JP2014006272 W JP 2014006272W WO 2016024305 A1 WO2016024305 A1 WO 2016024305A1
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Prior art keywords
metal plate
coated metal
top coat
film
gloss
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PCT/JP2014/006272
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English (en)
French (fr)
Japanese (ja)
Inventor
原　丈人
上田　耕一郎
健二 坂戸
裕樹 山口
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日新製鋼株式会社
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Application filed by 日新製鋼株式会社 filed Critical 日新製鋼株式会社
Priority to RU2017107362A priority Critical patent/RU2665518C1/ru
Priority to US15/503,161 priority patent/US20170226645A1/en
Priority to EP14899841.2A priority patent/EP3181352B1/en
Priority to KR1020177005085A priority patent/KR102323367B1/ko
Priority to ES14899841T priority patent/ES2779418T3/es
Priority to CN201480082611.3A priority patent/CN107073896B/zh
Publication of WO2016024305A1 publication Critical patent/WO2016024305A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/002—Pretreatement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/08—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of metal, e.g. sheet metal
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/12—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements of metal or with an outer layer of metal or enameled metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm

Definitions

  • the present invention relates to a coated metal plate for exterior, a manufacturing method thereof, and an exterior building material.
  • the coated metal plate is excellent in versatility, design and durability, and is used in various applications.
  • a gloss modifier is usually blended in the top coat film on the surface of the painted metal plate mainly from the viewpoint of design.
  • Silica particles are usually used for the gloss modifier in the coated metal plate for exterior building materials.
  • the particle size of the silica particles is usually defined by the average particle size.
  • the average particle diameter of the silica particles as the gloss adjusting agent in the coated metal plate is usually 3 to 30 ⁇ m, although depending on the color and application (see, for example, Patent Document 1 (paragraph 0018)).
  • ⁇ ⁇ Chromate-based coated steel sheets are used for painted metal sheets for exterior building materials.
  • efforts have been made to improve the moldability and the corrosion resistance of the cut end face, and the chromate-based coated steel sheet has long-term durability.
  • legal regulations that prohibit the use of ingredients that have a negative impact on the environment or are likely to be possible are being considered.
  • a coated metal plate it has been studied to limit the use of a hexavalent chromium component that is widely used as a rust preventive component in the near future.
  • Various studies have been conducted on chromate-free coated steel sheets, including pre-coating treatments and optimization of anti-corrosion pigments, and properties that are comparable to chromate-based coated steel sheets can be obtained at the forming and cutting end surfaces. .
  • the flat part corrosion resistance was not a big problem, but in the chromate-free coated steel sheet, the corrosion in the flat part may be remarkable, and in particular, silica particles were used as the gloss modifier.
  • corrosion such as spot rust and swelling of the coating film may occur in the flat portion earlier than the assumed years of use.
  • the object of the present invention is to have a flat design corrosion resistance that is equal to or better than a coated metal plate including a metal plate that has been chromate rust-proofed, even if it is chromate-free, while having the desired design with adjusted gloss. It is to provide a painted metal plate and an exterior building material.
  • FIG. 2 is a photomicrograph of the corroded portion of the flat portion of the chromate-free painted metal plate.
  • part A is a part where silica particles as a gloss adjusting agent are exposed from the top coat film
  • part B is a part where the silica particles are dropped from the top coat film.
  • FIG. 3 is a reflection electron micrograph of the cross section along the straight line L in FIG. 2 of the A part of the painted metal plate
  • FIG. 4 is the B part of the painted metal plate in FIG. It is a reflection electron micrograph of the cross section along the straight line L.
  • FIG. 3 clearly shows that the silica particles exposed on the surface of the top coating film are cracked
  • FIG. 4 shows that the holes in the top coating film from which the silica particles have fallen are corroded on the metal plate. It clearly shows that this is the starting point.
  • the corrosion is caused by cracking, disintegrating, or dropping off of the gloss adjusting agent of the top coat film.
  • the gloss modifier exposed from the top coating film which was depleted by actual use, was cracked, collapsed, and dropped from the top coating film.
  • the silica particles defined by the average particle diameter include particles that are considerably larger than the average particle diameter with respect to the thickness of the top coat film. It was confirmed that For example, when the present inventors observed the silica particle whose average particle diameter is 3.3 micrometers among the commercially available silica particles used for the said gloss regulator with an electron microscope, silica particles with a particle diameter of about 15 micrometers are found. It was confirmed that it was included (FIG. 5). Furthermore, when the present inventors observed the surface (B part in FIG. 6A) of the said silica particle, it confirmed that the countless fine space
  • the present inventors generally have a coating film made of a fluororesin generally excellent in weather resistance, although it is gentler than a coating film made of a normal resin such as polyester, but the same as described above. It was confirmed that abrasion of the top coat film and loss of the gloss modifier occurred (FIGS. 7A and 7B).
  • FIG. 7A the holes formed in the top coat film are indicated by black dots.
  • FIG. 7B the hole is caused by the gloss adjusting agent falling off from the top coat film.
  • the present inventors paid attention to the fact that such large particle size aggregated particles cause a decrease in corrosion resistance, and by using a gloss adjusting agent having a specific particle size with respect to the film thickness of the top coat film, The present inventors have found that corrosion resistance equal to or higher than the corrosion resistance obtained by using a chromate-based chemical conversion treatment and the use of a chromium-containing anticorrosive pigment in an undercoat film was completed.
  • this invention relates to the following coating metal plates and exterior building materials.
  • a coated metal plate having a metal plate and a top coat film disposed on the metal plate, wherein the top coat film is made of a fluororesin, and the top coat film has pores.
  • the gloss adjusting agent is contained in the top coat film in an amount of 0.01 to 15% by volume, and the number average particle diameter of the gloss adjusting agent is R ( ⁇ m),
  • the film thickness of the coating film is T ( ⁇ m)
  • the 97.5% particle size in the cumulative particle size distribution based on the number of gloss modifiers is D 97.5 ( ⁇ m)
  • the upper limit particle size in the number particle size distribution of the gloss modifier Is a coated metal plate that satisfies the following formula.
  • this invention relates to the manufacturing method of the following coated metal plates.
  • the gloss modifier is a particle having pores, the gloss average agent has a number average particle diameter of R ( ⁇ m), the film thickness of the top coat film is T ( ⁇ m), and the gloss modifier has a number standard.
  • the exposure and cracking of the gloss adjusting agent during the expected service life are prevented.
  • it has the desired design with adjusted gloss, and even if it is chromate-free, it has excellent flat part corrosion resistance equivalent to or better than a painted metal plate including a metal plate treated with chromate rust.
  • a painted metal plate is provided.
  • FIG. 3 is a reflection electron micrograph of a cross section along a straight line L in FIG.
  • FIG. 3 is a reflection electron micrograph of a cross section along a straight line L in FIG. 2 of a portion B of the coated metal plate shown in FIG. 2.
  • FIG. 6A is an electron micrograph of commercially available silica particles, and FIG.
  • FIG. 6B is an electron micrograph showing the portion B in FIG. 6A further enlarged.
  • FIG. 7A is an electron micrograph showing a part of a flat portion of a chromate-free and fluororesin-coated metal sheet coated with a metal plate with an actual use of 7.5 years magnified 250 times, and FIG. It is the electron micrograph which expands and shows a part of part 1,000 times.
  • FIG. 8A is a diagram schematically showing a cross section of a coated metal plate immediately after the top coating is applied
  • FIG. 8B is a diagram schematically showing a cross section of the coated metal plate after the top coating is baked. .
  • the said coating metal plate has a metal plate and the top coat film arrange
  • the metal plate can be selected from known metal plates as long as the effects of the present embodiment can be obtained.
  • the metal plate include cold rolled steel sheet, galvanized steel sheet, Zn—Al alloy plated steel sheet, Zn—Al—Mg alloy plated steel sheet, aluminum plated steel sheet, stainless steel sheet (austenite, martensite, ferrite, ferrite) -Including martensite two-phase system), aluminum plates, aluminum alloy plates, copper plates and the like.
  • the metal plate is preferably a plated steel plate from the viewpoint of corrosion resistance, weight reduction and cost effectiveness.
  • the plated steel sheet is preferably a molten 55% Al—Zn alloy plated steel sheet, a Zn—Al—Mg alloy plated steel sheet or an aluminum plated steel sheet from the viewpoint of corrosion resistance and suitability as an exterior building material.
  • the metal plate preferably has a chemical conversion treatment film on its surface from the viewpoint of improving the adhesion and corrosion resistance of the coated metal plate.
  • the chemical conversion treatment is a kind of pretreatment for coating a metal plate, and the chemical conversion treatment film is a layer of a composition formed by the pretreatment for coating.
  • the above metal plate is preferably subjected to non-chromate rust prevention treatment from the viewpoint of reducing the environmental load in the production and use of the coated metal plate, and the chromate rust prevention treatment is preferably applied to the corrosion resistance. From the viewpoint of further improving the ratio.
  • Examples of the chemical conversion coating by the non-chromate antirust treatment include Ti-Mo composite coating, fluoroacid coating, phosphate coating, resin coating, resin and silane coupling agent coating, silica coating, silica And silane coupling agent-based coatings, zirconium-based coatings, and zirconium and silane coupling agent-based coatings.
  • the amount of the Ti—Mo composite coating on the metal plate is preferably 10 to 500 mg / m 2 in terms of total Ti and Mo, and the amount of the fluoroacid coating is fluorine. It is preferably 3 to 100 mg / m 2 in terms of total metal elements, or the amount of the phosphate coating deposited is preferably 0.1 to 5 g / m 2 in terms of phosphorus elements.
  • the amount of the resin-based film deposited is preferably 1 to 500 mg / m 2 in terms of resin, and the amount of the resin and the silane coupling agent-based film deposited is 0.1 to 50 mg / m 2 in terms of Si.
  • the adhesion amount of the silica-based coating is preferably in terms of Si is 0.1 ⁇ 200 mg / m 2
  • the amount of the zirconium-based coating is preferably 0.1 to 100 mg / m 2 in terms of Zr
  • the zirconium and silane coupling agent-based coating is preferably 0.1 to 200 mg / m 2 .
  • the adhesion amount is preferably 0.1 to 100 mg / m 2 in terms of Zr.
  • the chromate rust prevention treatment examples include coating-type chromate treatment and phosphoric acid-chromic acid treatment. From the above viewpoint, the coating amount of the chromate rust preventive treatment on the metal plate is preferably 20 to 80 g / m 2 in terms of chromium element.
  • the top coat film is made of a fluororesin. As long as the top coat film contains a fluororesin as a main component, it may further contain other resins.
  • the top coat film may be composed of 50 to 85% by mass of a fluororesin and the remaining acrylic resin of the resin component in the top coat film.
  • the resins in the resin component may be bonded to each other or may not be bonded.
  • the fluororesin is excellent in durability, chemical resistance, heat resistance, abrasion resistance, stain resistance, etc. Among them, it has high workability and mechanical strength, and therefore it may be polyvinylidene fluoride (PVDF). preferable.
  • PVDF polyvinylidene fluoride
  • the acrylic resin contributes to the improvement of coating film adhesion.
  • the acrylic resin is preferably a thermoplastic acrylic resin or a thermosetting acrylic resin having compatibility with polyvinylidene fluoride.
  • the acrylic resin include polymers of acrylic monomers such as methyl methacrylate (MMA), methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), butyl methacrylate (BMA), Or the copolymer of the monomer containing the said acrylic monomer is contained.
  • the top coat film is composed mainly of a resin component made of polyvinylidene fluoride and an acrylic resin.
  • the mass ratio (PVDF: AR) of polyvinylidene fluoride (PVDF) and acrylic resin (AR) is preferably in the range of 50:50 to 85:15. If the weight ratio of polyvinylidene fluoride is too low, the properties of the fluororesin such as weather resistance, corrosion resistance, and contamination resistance may not be fully exerted. If the weight ratio of polyvinylidene fluoride is too high, The adhesion of the film may decrease, and the workability of the coated metal plate may decrease.
  • the film thickness T of the top coat film is 3 to 40 ⁇ m. If the film thickness T of the topcoat film is too thick, it may cause the occurrence of coating defects (waki), decrease in productivity and increase in manufacturing cost, and if it is too thin, the desired design and expected design properties. Flat part corrosion resistance may not be obtained.
  • the film thickness T of the top coat film is: From the above viewpoint, for example, it is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, and further preferably 25 ⁇ m or more.
  • the film thickness T of the top coat film is preferably 35 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • the film thickness T of the top coat film is, for example, the average value of the distances from the bottom surface to the surface at a plurality of locations of the top coat film.
  • the film thickness T of the top coating film can be determined further considering the presence of the other coating film.
  • the film thickness T of the topcoat film is preferably 10 to 30 ⁇ m from the viewpoints of design properties, corrosion resistance, and workability.
  • the film thickness T of the topcoat film is preferably 3 to 15 ⁇ m from the above viewpoint.
  • the film thickness T of the top coat film is preferably thicker when the color of the top coat film is bright from the viewpoint of the design properties of the coated metal plate, and can be thinner when the color of the top coat film is dark. .
  • the film thickness T of the top coat film can be 20 ⁇ m or less, and if the L value of the top coat film is more than 80, for example.
  • the film thickness T is preferably 25 ⁇ m or more.
  • the film thickness T of the top coat film is such that the color of the top coat film is close to the color of the surface of the steel sheet before the top coat film is formed (for example, the undercoat film described later) from the viewpoint of the design properties of the coated metal sheet. It can be made as thin as possible. For example, if the absolute value ⁇ L of the difference between the L value of the top coat film and the L value of the surface color of the steel sheet before the coating is formed is 10 or less, the film thickness T of the top coat film is not clear. If ⁇ L is 20 or less, the film thickness T can be 13 ⁇ m or less, and if ⁇ L is 50 or less, the film thickness T can be 15 ⁇ m or less.
  • the L value can be obtained by calculation using a Hunter color difference equation from the measurement result obtained by a commercially available spectrocolorimeter (for example, “CM3700d” manufactured by Konica Minolta Optics, Inc.).
  • a commercially available spectrocolorimeter for example, “CM3700d” manufactured by Konica Minolta Optics, Inc.
  • the top coat film contains a gloss modifier.
  • the gloss modifier is used to properly roughen the surface of the top coat film for the purpose of achieving the desired gloss on the coated metal plate or adjusting the gloss variation between production lots. Blended in to bring the desired appearance with luster to the painted metal sheet.
  • the number average particle diameter R of the gloss adjusting agent is 1.0 ⁇ m or more. If the gloss modifier is too small, the gloss of the top coat film is too high, and the desired design properties may not be obtained. Thus, the number average particle diameter R of the gloss adjusting agent can be appropriately determined within a range satisfying the following formula according to the intended designability (glossiness) of the coated metal plate. If it is too high, the gloss of the top coat film is too low and the desired design properties cannot be obtained. For example, from the viewpoint of obtaining a coated metal plate having a flat portion corrosion resistance and a glossiness of 20 to 85 at 60 °, the number average particle size R of the gloss modifier is preferably 2.0 ⁇ m or more, and preferably 3.0 ⁇ m or more.
  • the number average particle diameter can be confirmed by observing the cross section of the top coat film, or by an image analysis method and a Coulter method (for example, using a precision particle size distribution measuring device “Multisizer 4” manufactured by Beckman Coulter, Inc.). It is possible to measure.
  • the number average particle diameter R of the gloss adjusting agent can be determined according to the film thickness T of the top coating film.
  • the number average particle diameter R of the gloss adjusting agent is selected from the viewpoints of design properties, corrosion resistance, and workability due to the desired gloss. It is preferably 0 ⁇ m or more.
  • the number average particle size R of the gloss modifier is 1.0 ⁇ m or more from the above viewpoint. It is preferable.
  • the content of the gloss modifier in the top coat film is 0.01 to 15% by volume. When there is too much the said content, the glossiness of top coat film is too low, and process part adhesiveness falls. If the content is too small, the gloss cannot be controlled, and therefore the desired designability may not be obtained even if the content is large or small.
  • the content of the gloss adjusting agent in the top coat film is preferably 0.05% by volume or more, and 0.1 volume. % Or more is more preferable.
  • the content of the gloss adjusting agent in the top coat film is preferably 13% by volume or less, and more preferably 10% by volume or less. The content can be confirmed by measuring the ash content of the top coat film, collecting the gloss adjusting agent by dissolving the top coat film, image analysis of cross-sectional images in which elements are identified at a plurality of locations, and the like.
  • the gloss modifier is a particle having pores (hereinafter also referred to as “pore particle”).
  • the pore particles include aggregates in which primary particles are chemically bonded, aggregates in which primary particles are physically bonded, and porous particles.
  • the porous particles have a porous structure at least inside the particles.
  • the gloss adjusting agent may be composed of only the pore particles or may contain particles other than the pore particles.
  • the pore particles may be inorganic particles or organic particles, and can be selected from known pore particles used as a gloss adjusting agent as long as the following formula is satisfied.
  • the material of the pore particles include silica, calcium carbonate, barium sulfate, polyacrylonitrile, and a calcium carbonate-calcium phosphate complex.
  • the gloss adjusting agent is preferably silica particles from the viewpoint of having a high gloss adjusting effect on the coated metal plate.
  • the coated metal plate has a number average particle diameter of the gloss modifier of R ( ⁇ m), a film thickness of the top coat film of T ( ⁇ m), and a cumulative particle size distribution based on the number of gloss modifiers (hereinafter referred to as “number”
  • number a number average particle diameter of the gloss modifier of R ( ⁇ m)
  • the 97.5% particle diameter in the “particle size distribution” is D 97.5 ( ⁇ m)
  • the Ru is 1.2 T or less.
  • the “upper limit particle size (Ru)” is a particle size when the particle size distribution curve in the number particle size distribution is not less than the number average particle size R and overlaps the baseline.
  • D 97.5 is a substantial index of the particle size of the gloss modifier that can achieve the effects of the present invention.
  • D 97.5 / T is too large, the pore particles are exposed by attrition due to actual use of the top coating film, may not be obtained the desired flat portion corrosion resistance, is D 97.5 / T If it is too small, the desired glossiness may not be obtained.
  • D 97.5 / T is preferably 0.15 or more, more preferably 0.3 or more, and 0 More preferably, it is 4 or more.
  • D 97.5 / T is preferably 0.7 or less, and is 0.5 or less. It is more preferable.
  • grains larger than 0.9T in the said gloss adjusting agent are too few to have a substantial influence on flat part corrosion resistance.
  • the gloss modifier is generally irregular and is usually flat to some extent.
  • the gloss adjusting agent in the top coating film is usually more easily oriented in the horizontal direction than the vertical direction by applying the below-described top coating paint. This is probably because the particle size in the film thickness direction is usually smaller than the major axis (for example, 1.2 T) of the gloss modifier.
  • Ru is preferably less than T, more preferably 0.9T or less, and 0.7T or less. Is more preferable.
  • R, D 97.5 and Ru can be obtained from the number particle size distribution of the gloss modifier.
  • the aspect smaller than the average particle diameter R in the number particle size distribution of the gloss modifier may be in any form as long as the condition of the particle size distribution is satisfied.
  • a commercially available product or a classified product thereof can be used as the gloss adjusting agent that satisfies the conditions relating to the particle size distribution.
  • the gloss modifier may not satisfy the above-mentioned particle size conditions (for example, there are coarse particles having a particle size larger than 1.2 T).
  • the above conditions may be deviated during the manufacturing process.
  • the above-mentioned top coat film may further contain other components other than the above-described resin and gloss adjusting agent as long as the effect in the present embodiment can be obtained.
  • the top coat film may further contain a colorant.
  • colorants include inorganic pigments such as titanium oxide, calcium carbonate, carbon black, iron black, iron oxide yellow, titanium yellow, bengara, bitumen, cobalt blue, cerulean blue, ultramarine blue, cobalt green, molybdenum red; CoAl, Composite oxide fired pigments containing metal components such as CoCrAl, CoCrZnMgAl, CoNiZnTi, CoCrZnTi, NiSbTi, CrSbTi, FeCrZnNi, MnSbTi, FeCr, FeCrNi, FeNi, FeCrNiMn, CoCr, Mn, Co, SnZnTi; Al flakes, resin-coated Al flakes , Ni flakes, stainless
  • the top coat film may further contain extender pigments.
  • the extender pigment include barium sulfate and titanium oxide.
  • the extender pigment is sufficiently smaller than the gloss control agent.
  • the extender pigment has a number average particle diameter of 0.01 to 1 ⁇ m.
  • the content of the extender pigment in the top coat film is, for example, 0.1 to 15% by volume.
  • the above-mentioned top coat film may further contain a lubricant from the viewpoint of preventing galling in the top coat film during the processing of the coated metal plate.
  • a lubricant examples include organic waxes such as fluorine wax, polyethylene wax, styrene wax, and polypropylene wax, and inorganic lubricants such as molybdenum disulfide and talc.
  • the content of the lubricant in the top coat film is, for example, 0 to 10% by volume.
  • the top coating film is prepared by a known method in which a coating for a top coating film (top coating) is applied to the surface of the metal plate or the surface of the undercoating film described below, dried, and cured as necessary. Is done.
  • the topcoat paint contains the above-mentioned topcoat film material, but may further contain other components in addition to the material as long as the effects of the present embodiment can be obtained.
  • the top coat may further contain a curing agent.
  • the curing agent crosslinks the above-mentioned fluororesin or acrylic resin at the time of curing (baking) when producing the top coat film.
  • the type of the curing agent can be appropriately selected from the above-described crosslinking agents and known curing agents according to the type of resin used and the baking conditions.
  • Examples of the curing agent include melamine compounds, isocyanate compounds, and combinations of melamine compounds and isocyanate compounds.
  • Examples of the melamine compound include an imino group type, a methylol imino group type, a methylol group type or a fully alkyl group type melamine compound.
  • the isocyanate compound may be aromatic, aliphatic, or alicyclic, and examples include m-xylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, and block compounds thereof.
  • the top coat film may further contain a curing catalyst as appropriate as long as it does not affect the storage stability of the top coat.
  • the content of the curing agent in the top coat film is, for example, 10 to 30% by volume.
  • the top coat film may appropriately contain 10% by volume or less of an ultraviolet absorber (UVA) or a light stabilizer (HALS) in order to further improve the weather resistance.
  • UVA ultraviolet absorber
  • HALS light stabilizer
  • the top coat film may contain a hydrophilizing agent for preventing rain streak stains, for example, 30% by volume or less of a partial hydrolysis condensate of tetraalkoxysilane.
  • the coated metal plate may have further components as long as the effects of the present embodiment are exhibited.
  • the said coated metal plate further has an undercoat film between the said metal plate and the said top coat film from a viewpoint of improving the adhesiveness and corrosion resistance of the top coat film in a coated metal plate.
  • the said undercoat coating film is arrange
  • the above-mentioned undercoat film is made of resin.
  • the resin include epoxy resin, polyester, epoxy-modified polyester resin, acrylic resin, and phenoxy resin.
  • the undercoat coating film may further contain a rust preventive pigment, a color pigment, a metallic pigment, and the like.
  • the rust preventive pigment include non-chromium rust preventive pigments such as modified silica, vanadate, magnesium hydrogen phosphate, magnesium phosphate, zinc phosphate, and aluminum polyphosphate, strontium chromate, and zinc chromate. , Chromium-based anticorrosive pigments such as barium chromate and calcium chromate are included.
  • the color pigment include titanium oxide, carbon black, chromium oxide, iron oxide, bengara, titanium yellow, cobalt blue, cobalt green, aniline black, and phthalocyanine blue.
  • the metallic pigment include aluminum flake (non-leafing type), bronze flake, copper flake, stainless steel flake and nickel flake.
  • the extender pigment include barium sulfate, titanium oxide, silica, and calcium carbonate.
  • the content of the pigment in the undercoat coating film can be determined as appropriate within the range where the effect of the present embodiment can be obtained.
  • the content of the rust preventive pigment in the primer coating film is, for example, It is preferably 10 to 70% by volume.
  • the coated metal plate may further include an intermediate coating film between the undercoat film and the topcoat film from the viewpoint of improving the adhesion and corrosion resistance of the topcoat film on the coated metal plate.
  • the intermediate coating film is made of resin.
  • the resin include fluororesins such as polyvinylidene fluoride, polyester, polyester-modified silicone, acrylic resin, polyurethane, and polyvinyl chloride.
  • the intermediate coating film may further contain an additive such as a rust preventive pigment, a coloring pigment, and a metallic pigment as appropriate within the range in which the effect of the present embodiment can be obtained, similarly to the undercoat coating film. .
  • FIG. 8A is a diagram schematically showing a cross section of the coated metal plate immediately after the top coating is applied
  • FIG. 8B is a diagram schematically showing a cross section of the coated metal plate after the coating is baked.
  • the gloss adjusting agent 15 is a surface state of the coating film 12 of the coating material when the top coating material is applied to the base steel plate 11 (for example, a plated steel plate or a plated steel plate and an undercoat coating film). Does not substantially affect For this reason, the desired gloss is not usually exhibited before baking the paint. on the other hand. After the paint is baked, the volatile components in the paint are volatilized, so the film thickness T of the top coat film 22 is thinner than the thickness t of the paint film 12. For this reason, the convex part by the gloss adjusting agent 15 is formed in the surface of the top coat film 22, and the top coat film 22 expresses desired glossiness (in this invention, gloss of enamel tone).
  • the painted metal plate according to the present embodiment is a chromate-free and chromate-based painted metal plate.
  • Chroate-free means that the coated metal plate does not substantially contain hexavalent chromium.
  • the fact that the above-mentioned coated metal plate is “chromate-free” means that, for example, any of the above-described metal plate, chemical conversion film, undercoat film and topcoat film is a metal in which the topcoat film or undercoat film is produced alone.
  • Four test pieces of 50 mm ⁇ 50 mm were cut out from the plate, immersed in 100 mL of boiling pure water for 10 minutes, and then hexavalent chromium eluted in the pure water was added to 2.4.1 of JIS H8625 appendix.
  • the coated metal plate does not elute hexavalent chromium into the environment, and exhibits sufficient corrosion resistance at the flat portion.
  • the “flat part” refers to a part that is covered with the top coating film of the metal plate and is not deformed by bending, drawing, overhanging, embossing, roll molding, or the like.
  • the coated metal plate is suitable for a painted metal plate having enamel luster.
  • Enamel gloss refers to a glossiness of 20 to 85 at 60 °. If the glossiness is too low, the matte appearance becomes dominant and enamel-like glossiness may not be obtained. If the glossiness is too high, the glossiness cannot be controlled and the reproducibility of the paint appearance is obtained. Absent. The glossiness is adjusted by the average particle diameter of the gloss adjusting agent, the content in the top coat film, or the like.
  • the coated metal plate is formulated with a different intention from the gloss modifier, such as a matting agent, and does not contain particles (large particles) having a larger particle size than the gloss modifier. From the viewpoint of obtaining desired design properties such as enamel gloss. However, the coated metal plate may further contain the large particles as long as the effects of the present embodiment can be obtained.
  • the large particles are preferably primary particles from the viewpoint of maintaining flat portion corrosion resistance.
  • the coated metal plate includes a first step of applying a top coating containing the fluororesin and the gloss modifier on the metal plate, and forming the top coating by curing the coating of the top coating. And a second step.
  • the top coat may be applied directly to the surface of the metal plate, may be applied to the chemical conversion film formed on the surface of the metal plate, or the painted metal. You may apply
  • the top coat is prepared, for example, by dispersing the above-mentioned top coat material in a solvent.
  • the coating material may contain a solvent, a crosslinking agent, and the like.
  • the solvent include hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; ethers such as cellosolve; and ketones such as methyl isobutyl ketone, methyl ethyl ketone, isophorone and cyclohexanone.
  • the top coat is applied by a known method such as roll coating, curtain flow coating, spray coating, or dip coating.
  • the amount of the top coat applied is appropriately adjusted according to the desired film thickness T of the top coat.
  • the gloss adjusting agent contained in the top coat satisfies the above-mentioned size condition.
  • the top coating satisfying the above condition is performed by subjecting the top coating to a process of pulverizing particles in the top coating. It is possible to obtain Examples of the above-mentioned “treatment for crushing particles” include treatment by a roller mill. More specifically, by appropriately setting the clearance between the rollers of the roller mill and the processing time so that the Ru is less than 1.2T, it is possible to obtain the top coat that satisfies the above conditions. is there.
  • the second step can be performed by, for example, a known method of baking the top coat onto a metal plate.
  • the metal plate to which the top coat is applied is heated so that the ultimate temperature is 200 to 250 ° C.
  • the method for producing a coated metal plate may further include other steps than the first step and the second step described above as long as the effect of the present invention is obtained.
  • the other steps include a step of forming a chemical conversion coating, a step of forming an undercoat coating, and a step of forming an intermediate coating.
  • the chemical conversion coating is applied to the surface of the metal plate by a known method such as a roll coating method, a spin coating method, or a spraying method, and the metal plate is applied after coating. It can be formed by drying without washing with water. From the viewpoint of productivity, the drying temperature and drying time of the metal plate are preferably, for example, 60 to 150 ° C. and 2 to 10 seconds at the ultimate temperature of the metal plate.
  • the above-mentioned undercoat film is prepared by applying a paint for an undercoat film (undercoat paint).
  • the undercoat paint may contain a solvent, a crosslinking agent, and the like.
  • the solvent include the compounds exemplified as the solvent for the top coat.
  • the crosslinking agent include melamine resins and isocyanate resins that crosslink the above-described resins.
  • the undercoat paint is prepared by uniformly mixing and dispersing the aforementioned materials.
  • the undercoat paint is applied to the metal plate by a known method described above for the overcoat paint, for example, in an application amount that provides a dry film thickness of 1 to 10 ⁇ m (preferably 3 to 7 ⁇ m).
  • the coating film of the paint is produced by baking on the metal plate, for example, by heating the metal plate at a temperature of 180 to 240 ° C. at the temperature reached by the metal plate.
  • the above-mentioned intermediate coating film is also produced by applying a coating for an intermediate coating film (intermediate coating) in the same manner as the undercoating film.
  • the intermediate coating material may also contain the solvent, the crosslinking agent, and the like in addition to the material of the intermediate coating film.
  • the intermediate coating is prepared by uniformly mixing and dispersing the materials described above.
  • the intermediate coating is applied to the undercoating film by a known method as described above in a coating amount of 3 to 20 ⁇ m (preferably 5 to 15 ⁇ m) in total of the dry film thickness of the coating and the film thickness of the undercoating film. It is preferable from the viewpoint of workability.
  • the coating film of the paint is produced by baking on the metal plate, for example, by heating the metal plate at a temperature of 180 to 240 ° C. at the temperature reached by the metal plate.
  • the exterior of the coated metal plate is suitable for exterior use. “Exterior” refers to a portion that is exposed to the outside air, such as a roof, a wall, an accessory, a signboard, and an outdoor installation device, and is used for a portion that can be irradiated with sunlight or its reflected light. Examples of the exterior coated metal plate include a painted metal plate for exterior building materials.
  • the coated metal plate is formed into an exterior building material such as an exterior building material by known processes such as bending, drawing, overhanging, embossing, and roll molding.
  • the said exterior building material is comprised with the said coating metal plate.
  • the exterior building material may further include another configuration within a range in which the above effect can be obtained.
  • the exterior building material may further have a configuration that is provided for appropriate installation in actual use of the exterior building material. Examples of such a configuration include a member for fixing the exterior building material to the building, a member for connecting the exterior building materials to each other, a mark indicating the direction when the exterior building material is attached, and heat insulation. Foam sheet and foam layer. These configurations may be included in the above-described exterior coated metal plate.
  • the gloss modifier (pore particles) is sufficiently confined in the top coat film.
  • the particle size of the gloss adjusting agent in the top coat film in the film thickness direction of the top coat film tends to be sufficiently small as the particle shape is flat.
  • about 97.5% by number, and most of the above gloss modifiers have a sufficiently small particle size of “0.9 T” or less than the film thickness T of the top coat film. Therefore, even if the resin of the top coat film is gradually depleted from the surface of the top coat film due to actual use in exterior applications, the above top coat is not exposed within the expected years of use. It is possible to design a coating film.
  • the said coated metal plate is chromate-free (if the said metal plate is non-chromate rust-proofing treatment), it expresses at least the flat part corrosion resistance equivalent to the conventional coated metal plate that has been chromated, If the chromate treatment is performed, the flat portion corrosion resistance equal to or higher than that of the conventional coated metal plate subjected to the chromate treatment is exhibited.
  • Examples of the “chromate treatment” of the coated metal plate in the present embodiment include the use of an undercoat film containing a chromate rust preventive pigment in addition to the chromate rust preventive treatment of the metal plate.
  • Examples of ⁇ treated coated metal plate '' include a coated metal plate having a non-chromate rust-proof metal plate and an undercoat film containing a chromate-based anti-rust pigment, a chromate rust-proof metal plate and a chromate. And a coated metal plate having an undercoating film containing no rust preventive pigment, and a coated metal plate having a chromate rust preventive-treated metal plate and an undercoating film containing a chromate rust preventive pigment.
  • the present embodiment has a metal plate and a top coat film disposed on the metal plate, the top coat film is made of a fluororesin, and Particles having pores (pore particles) are contained as a gloss modifier, and the content of the gloss modifier in the top coat film is 0.01 to 15% by volume, and the number average particle of the gloss modifier
  • the diameter is R ( ⁇ m)
  • the film thickness of the top coat film is T ( ⁇ m)
  • the 97.5% particle diameter in the number particle size distribution of the gloss modifier is D 97.5 ( ⁇ m)
  • the number of the gloss modifier Since the following formula is satisfied when the upper limit particle size in the particle size distribution is Ru ( ⁇ m), a coated metal plate having sufficient flat portion corrosion resistance can be provided even if it is chromate-free.
  • the Ru of less than T is more effective from the viewpoint of further improving the flat portion corrosion resistance of the coated metal plate or from the viewpoint of further extending the life of the coated metal plate having sufficient flat portion corrosion resistance. is there.
  • the non-chromate anti-rust treatment is applied to the metal plate, and the fact that the painted metal plate is chromate-free is more effective from the viewpoint of reducing the environmental load in the use or production of the painted metal plate. And it is more effective that the said metal plate is subjected to the chromate rust prevention treatment from the viewpoint of further improving the flat portion corrosion resistance of the coated metal plate.
  • the gloss adjusting agent is silica particles is more effective from the viewpoint of inexpensively producing a coated metal plate having the desired design properties.
  • the coating metal plate further having an undercoat film between the metal plate and the top coat film is more effective from the viewpoint of improving the adhesion and corrosion resistance of the top coat film on the paint metal plate, It is more effective from the above viewpoint to further have an intermediate coating film between the undercoating film and the top coating film.
  • the top coating film is composed of a resin component as a main component composed of polyvinylidene fluoride and an acrylic resin means that the properties of the fluororesin such as weather resistance, corrosion resistance, and contamination resistance, This is even more effective from the viewpoint of developing both the properties of the acrylic resin such as adhesion.
  • the fact that the above-mentioned coated metal plate is an exterior coated metal plate is more effective from the viewpoint of reducing the environmental load due to elution of chromium during actual use.
  • the exterior building material composed of the above-mentioned coated metal plate can exhibit excellent flat portion corrosion resistance in actual use for 10 years or more even if it is chromate-free.
  • the method for producing a coated metal plate having the above-described metal plate and a top coat film disposed on the metal plate is obtained by applying the top coat paint containing the fluororesin and the gloss adjusting agent to the metal plate. And a step of curing the top coat film to form the top coat film, and the content of the gloss modifier in the top coat film is 0.01 to 15 volumes.
  • the gloss modifier is particles having pores, the number average particle diameter of the gloss modifier is R ( ⁇ m), the film thickness of the top coat film is T ( ⁇ m), and the gloss modifier
  • the 97.5% particle size in the number particle size distribution of D 97.5 ( ⁇ m) and the upper limit particle size distribution of the number particle size distribution of the gloss modifier is Ru ( ⁇ m)
  • the above gloss satisfying the following formula: Use a modifier. Therefore, even if it is chromate free, the coated metal plate which has the flat part corrosion resistance equivalent to or better than the coated metal plate including the metal plate subjected to the chromate rust prevention treatment can be provided.
  • the top coating material when the top coating material is subjected to a treatment for pulverizing particles in the top coating material, coarse particles that are unintentionally and irregularly present in the top coating film are substantially removed from the top coating material. Therefore, it is more effective from the viewpoint of improving the corrosion resistance of the flat portion of the coated metal plate.
  • Non-chromate anti-rust treatment liquid Hexafluorotitanic acid 55g / L Hexafluorozirconic acid 10g / L Aminomethyl-substituted polyvinylphenol 72g / L Water rest
  • the following primer coating of epoxy resin type is applied to the surface of the coating original plate 2, the chemical conversion treated steel sheet is heated so that the ultimate temperature of the plated steel sheet is 200 ° C., and the undercoat film has a dry film thickness of 5 ⁇ m.
  • the above-mentioned chromate-free plated steel sheet (painted original sheet 3) was obtained.
  • the clear paint is “NSC680” manufactured by Nippon Fine Coatings Co., Ltd.
  • the phosphate mixture is a mixture of magnesium hydrogen phosphate, magnesium phosphate, zinc phosphate, and aluminum tripolyphosphate.
  • the silica is an extender, and the average particle diameter is 5 ⁇ m. Furthermore, the above volume% is a ratio to the solid content in the undercoat paint.
  • the following intermediate coating material of polyester type is applied to the surface of the coating original plate 3, the chemical conversion treatment steel plate is heated so that the ultimate temperature of the plated steel plate is 220 ° C., and dried on the undercoat coating film.
  • the chromate-free plated steel sheet (coating original sheet 5) having an intermediate coating film thickness of 15 ⁇ m was obtained.
  • the above-mentioned fluororesin-based paint is a clear paint “Dick Flow C” manufactured by Nippon Fine Coatings Co., Ltd., and is a fluororesin (PVDF / AR) -based paint. Carbon black is a coloring pigment.
  • the volume% is a ratio with respect to the solid content in the intermediate coating.
  • the silica particle 1 (silica 1) is, for example, a classified product or a mixture thereof, and has a normal distribution-like particle size distribution.
  • the number average particle diameter R of the silica particles 1 is 7.0 ⁇ m, and D 97.5 in the number particle size distribution is 22.0 ⁇ m.
  • the upper limit particle size Ru in the number particle size distribution is 23.5 ⁇ m.
  • the clear paint 1 is a clear paint “Dick Flow C” manufactured by Nippon Fine Coatings Co., Ltd., and is a fluororesin (PVDF / AR) paint. Carbon black is a coloring pigment.
  • the following volume% is a ratio with respect to the solid content in the top coat.
  • the coated metal plate 1 is cut to expose its cross section, enclosed in an epoxy resin block, further polished, and the cross section taken with a scanning electron microscope.
  • R, D 97.5, and Ru were substantially the same as the above numerical values.
  • a coated metal plate 2 was produced in the same manner as the coated metal plate 1 except that the amount of the top coating was changed so that the dry film thickness T was 22 ⁇ m. Further, a coated metal plate 3 was produced in the same manner as the coated metal plate 1 except that the coating amount of the top coating was changed so that the dry film thickness T was 20 ⁇ m.
  • a coated metal plate 4 was produced in the same manner as the coated metal plate 1 except that the silica particles 2 were used in place of the silica particles 1 as the gloss modifier in the top coat.
  • the silica particle 2 is, for example, a classified product or a mixture thereof, R is 7.0 ⁇ m, D 97.5 is 22.0 ⁇ m, and Ru is 25.0 ⁇ m.
  • a coated metal plate 5 was produced in the same manner as the coated metal plate 1 except that the silica particles 3 were used in place of the silica particles 1 as the gloss modifier in the top coat.
  • the silica particle 3 is, for example, a classified product or a mixture thereof, R is 7.0 ⁇ m, D 97.5 is 22.0 ⁇ m, and Ru is 29.5 ⁇ m.
  • a coated metal plate 6 was produced in the same manner as the coated metal plate 1 except that the silica particles 4 were used in place of the silica particles 1 as the gloss modifier in the top coat.
  • the silica particle 4 is, for example, a classified product or a mixture thereof, R is 7.0 ⁇ m, D 97.5 is 22.0 ⁇ m, and Ru is 31.8 ⁇ m.
  • a coated metal plate 7 was produced in the same manner as the coated metal plate 1 except that the silica particles 5 were used in place of the silica particles 1 as the gloss adjusting agent in the top coat.
  • the silica particle 5 is, for example, a classified product or a mixture thereof, R is 7.0 ⁇ m, D 97.5 is 22.0 ⁇ m, and Ru is 33.8 ⁇ m.
  • a coated metal plate 8 was produced in the same manner as the coated metal plate 1 except that the silica particles 6 were used in place of the silica particles 1 as the gloss modifier in the top coat.
  • the silica particle 6 is, for example, a classified product or a mixture thereof, R is 5.0 ⁇ m, D 97.5 is 7.6 ⁇ m, and Ru is 9.5 ⁇ m.
  • a coated metal plate 9 was produced in the same manner as the coated metal plate 1 except that the silica particles 7 were used in place of the silica particles 1 as the gloss adjusting agent in the top coat.
  • the silica particle 7 is, for example, a classified product or a mixture thereof, R is 3.0 ⁇ m, D 97.5 is 5.6 ⁇ m, and Ru is 9.5 ⁇ m.
  • a coated metal plate 10 was prepared in the same manner as the coated metal plate 1 except that the silica particles 8 were used in place of the silica particles 1 as the gloss modifier in the top coat.
  • the silica particle 8 is, for example, a classified product or a mixture thereof, R is 1.5 ⁇ m, D 97.5 is 4.1 ⁇ m, and Ru is 9.5 ⁇ m.
  • a coated metal plate 11 was produced in the same manner as the coated metal plate 1 except that the silica particles 9 were used in place of the silica particles 1 as the gloss adjusting agent in the top coat.
  • the silica particle 8 is, for example, a classified product or a mixture thereof, R is 0.5 ⁇ m, D 97.5 is 2.1 ⁇ m, and Ru is 9.5 ⁇ m.
  • a coated metal plate 12 was produced in the same manner as the coated metal plate 8 except that the amount of the top coat applied was changed so that the dry film thickness T was 15 ⁇ m.
  • a coated metal plate 13 was produced in the same manner as the coated metal plate 8 except that the coating amount of the top coating was changed so that the dry film thickness T was 10 ⁇ m.
  • silica particle 10 is used instead of the silica particles 1 as the gloss modifier in the top coat and the amount of the top coat applied is changed so that the dry film thickness T is 3 ⁇ m.
  • the silica particle 10 is, for example, a classified product or a mixture thereof, R is 1.0 ⁇ m, D 97.5 is 2.0 ⁇ m, and Ru is 2.6 ⁇ m.
  • a coated metal plate 15 was produced in the same manner as the coated metal plate 14 except that the amount of the top coat applied was changed so that the dry film thickness T was 2 ⁇ m.
  • a coated metal plate 16 was produced in the same manner as the painted metal plate 8 except that the amount of top coat applied was changed so that the dry film thickness T was 35 ⁇ m. Further, a coated metal plate 17 was produced in the same manner as the coated metal plate 8 except that the coating amount of the top coating was changed so that the dry film thickness T was 38 ⁇ m. Further, a coated metal plate 18 was produced in the same manner as the coated metal plate 8 except that the coating amount of the top coating was changed so that the dry film thickness T was 40 ⁇ m. Further, a coated metal plate 19 was produced in the same manner as the coated metal plate 8 except that the coating amount of the top coating was changed so that the dry film thickness T was 41 ⁇ m.
  • a coated metal plate 20 was produced in the same manner as the coated metal plate 1 except that the silica particles in the top coat were not blended. Moreover, it replaced with the silica particle 1 for the glossiness modifier in top coat, and used the silica particle 11, and it was the same as that of the coating metal plate 1 except having changed the content of the silica particle in top coat to 0.005 volume%. Thus, a painted metal plate 21 was produced.
  • the silica particle 11 is, for example, a classified product or a mixture thereof, R is 7.0 ⁇ m, D 97.5 is 12.3 ⁇ m, and Ru is 20.0 ⁇ m.
  • a coated metal plate 22 was produced in the same manner as the coated metal plate 21 except that the content of silica particles in the top coat was changed to 0.01% by volume.
  • a coated metal plate 23 was produced in the same manner as the coated metal plate 21 except that the content of silica particles in the top coat was changed to 0.1% by volume.
  • a coated metal plate 24 was produced in the same manner as the painted metal plate 21 except that the content of silica particles in the top coat was changed to 10% by volume.
  • a coated metal plate 25 was produced in the same manner as the coated metal plate 21 except that the content of silica particles in the top coat was changed to 15% by volume.
  • a coated metal plate 26 was produced in the same manner as the painted metal plate 21 except that the content of silica particles in the top coat was changed to 20% by volume.
  • the coated metal is the same as the coated metal plate 1 except that the silica particles 11 are used instead of the silica particles 1 as the gloss adjusting agent in the top coat and a top coat film is formed on the painted original plate 1 instead of the coated original plate 3.
  • a plate 27 was produced.
  • a coated metal plate 28 was produced in the same manner as the coated metal plate 27 except that a top coat film was formed on the painted original plate 2 instead of the painted original plate 1.
  • a coated metal plate 29 was produced in the same manner as the painted metal plate 27 except that a top coat film was formed on the painted original plate 4 instead of the painted original plate 1.
  • a coated metal plate 30 was obtained in the same manner as the coated metal plate 29 except that the silica particles 2 were used in place of the silica particles 11 as the gloss modifier in the top coat. Further, a coated metal plate 31 was obtained in the same manner as the coated metal plate 29 except that the silica particles 3 were used in place of the silica particles 11 as the gloss adjusting agent in the top coat.
  • a coated metal plate 32 was obtained in the same manner as the coated metal plate 1 except that polyacrylonitrile (PAN) particles were used instead of the silica particles 1 of the top coat.
  • PAN polyacrylonitrile
  • the PAN particle is, for example, a classified product or a mixture thereof, R is 7.0 ⁇ m, D 97.5 is 12.3 ⁇ m, and Ru is 20.0 ⁇ m.
  • a coated metal plate 33 was obtained in the same manner as the coated metal plate 1 except that calcium carbonate-calcium phosphate composite (CaCPC) particles were used instead of the silica particles 1 of the top coat.
  • the CaCPC particle is, for example, a classified product or a mixture thereof, R is 7.0 ⁇ m, D 97.5 is 12.3 ⁇ m, and Ru is 20.0 ⁇ m.
  • the coated metal plate 1 is the same as the coated metal plate 1 except that the coated original plate 5 is used instead of the coated original plate 3, silica 10 is used instead of the silica 1, and the coating amount of the top coat is changed so that the dry film thickness T is 10 ⁇ m. Similarly, a painted metal plate 34 was produced.
  • Tables 1 and 2 show the values and the examples and comparative examples.
  • Table 3 shows the results of the above evaluation of the coated metal plates 1 to 34.
  • particles having a particle size R ′ of 0.8 T ⁇ m (20.0 ⁇ m) or more are removed, and silica particles A substantially free of particles of 20.0 ⁇ m or more are separately prepared, and 97.5 parts by volume of silica particles 12 is mixed with 2.5 volume parts of silica particles A, and is composed of 97.5 volume parts of silica particles 12 of 0.7 T or less and 2.5 volume parts of silica particles A of 0.8 T or less.
  • Silica particles (content ratio: 97.5 / 2.5) were obtained. This is designated as silica particles 13.
  • a coated metal plate 36 was produced in the same manner as the coated metal plate 1 except that the silica particles 13 were used in place of the silica particles 1 as the gloss modifier in the top coat.
  • silica particles having a particle size R ′ of 0.9 T ⁇ m (22.5 ⁇ m) or more are removed, and silica particles B that are substantially free of particles of 22.5 ⁇ m or more are separately prepared.
  • 97.5 parts by volume of silica particles 12 is mixed with 2.5 volume parts of silica particles B, and is composed of 97.5 volume parts of silica particles 12 of 0.7 T or less and 2.5 volume parts of silica particles B of 0.9 T or less.
  • Silica particles were obtained. This is referred to as silica particles 14.
  • a coated metal plate 37 was produced in the same manner as the coated metal plate 1 except that the silica particles 14 were used in place of the silica particles 1 as the gloss modifier in the top coat.
  • silica particles having a particle size R ′ of 1.0 T ⁇ m (25.0 ⁇ m) or more are removed, and silica particles C substantially free of particles of 25.0 ⁇ m or more are separately prepared.
  • 97.5 parts by volume of silica particles 12 is mixed with 2.5 volume parts of silica particles C, and is composed of 97.5 volume parts of silica particles 12 of 0.7 T or less and 2.5 volume parts of silica particles C of 1.0 T or less.
  • Silica particles were obtained. This is referred to as silica particles 15.
  • a coated metal plate 38 was produced in the same manner as the coated metal plate 1 except that the silica particles 15 were used instead of the silica particles 1 as the gloss adjusting agent in the top coat.
  • particles having a particle size R ′ of 1.1 T ⁇ m (27.5 ⁇ m) or more are removed, and silica particles D substantially free of particles of 27.5 ⁇ m or more are separately prepared, and 97.5 parts by volume of silica particles 12 is mixed with 2.5 volume parts of silica particles D, and is composed of 97.5 volume parts of silica particles 12 of 0.7 T or less and 2.5 volume parts of silica particles D of 1.1 T or less.
  • Silica particles were obtained. This is designated as silica particle 16.
  • a coated metal plate 39 was prepared in the same manner as the coated metal plate 1 except that the silica particles 16 were used in place of the silica particles 1 as the gloss adjusting agent in the top coat.
  • silica particles having a particle size R ′ of 1.2 T ⁇ m (30.0 ⁇ m) or more are removed, and silica particles E substantially free of particles of 30.0 ⁇ m or more are separately prepared.
  • 97.5 parts by volume of silica particles 12 is mixed with 2.5 volume parts of silica particles E, and is composed of 97.5 volume parts of silica particles 12 of 0.7 T or less and 2.5 volume parts of silica particles E of 1.2 T or less.
  • Silica particles were obtained. This is designated as silica particles 17.
  • the coated metal plate 40 was produced like the coated metal plate 1 except having used the silica particle 17 instead of the silica particle 1 for the gloss regulator in top coat.
  • silica particles F substantially free of particles of 32.5 ⁇ m or more are separately prepared.
  • 97.5 parts by volume of silica particles 12 is mixed with 2.5 volume parts of silica particles F, and is composed of 97.5 volume parts of silica particles 12 of 0.7 T or less and 2.5 volume parts of silica particles F of 1.3 T or less.
  • Silica particles were obtained. This is referred to as silica particles 18.
  • a coated metal plate 41 was prepared in the same manner as the coated metal plate 1 except that the silica particles 18 were used in place of the silica particles 1 as the gloss modifier in the top coat.
  • the coated metal plates 35 to 41 were evaluated for flat portion corrosion resistance by the method described above. Painted metal plates 35 to 41, type of coating original plate, type of gloss adjusting agent, R, D 97.5 , cut value, particle size R ', T of main component of added silica particles, content of gloss adjusting agent Table 5 shows the content ratio of the two types of silica particles and the evaluation results of the flat portion corrosion resistance.
  • silica particle 19 By changing the content ratio of the silica particles 12 and the silica particles E in the silica particles 17, 97.0 parts by volume of the silica particles 12 of 0.7 T or less and 3.0 parts by volume of the silica particles E of 1.2 T or less Silica particles composed of This is designated as silica particle 19.
  • a coated metal plate 42 was produced in the same manner as the coated metal plate 1 except that the silica particles 19 were used in place of the silica particles 1 as the gloss modifier in the top coat.
  • silica particle 20 A coated metal plate 43 was prepared in the same manner as the coated metal plate 1 except that the silica particles 20 were used in place of the silica particles 1 as the gloss modifier in the top coat.
  • the flat part corrosion resistance was evaluated by the test method of 2 cycles mentioned above. Painted metal plates 40, 42 and 43, types of coating original plate, types of gloss adjusting agent, R, D 97.5 , cut value, particle size R ′, T of main component of added silica particles, gloss adjusting agent Table 6 shows the content, the content ratio of the two types of silica particles, and the evaluation results of the flat portion corrosion resistance.
  • a coated metal plate 44 was produced in the same manner as the painted metal plate 41 except that the top coat paint of the painted metal plate 41 was used after being processed by a roller mill under the condition of pulverizing the silica particles F. And when the flat part corrosion resistance was evaluated by the method mentioned above about the coating metal plate 44, both determination of 1 cycle and 2 cycles was B.
  • the coated metal plates 2, 3, 6 and 7 had insufficient flat portion corrosion resistance. This is presumably because the gloss adjusting agent was too large with respect to the film thickness T of the top coat film and was exposed from the top coat film during the durability test due to photodegradation of the top coat film.
  • the coated metal plate 11 was too glossy, and the desired design (enamel-like gloss) was not obtained. This is presumably because the particle size of the gloss adjusting agent was too small.
  • the coated metal plate 15 has insufficient concealability, that is, the visibility of the top coat film is expressed only to such an extent that the undercoat (undercoat film) of the top coat film can be visually observed.
  • the design of the period was not obtained. For this reason, it judged that it was not worth performing the evaluation test of flat part corrosion resistance, and the said evaluation test was not implemented.
  • the reason why the above concealment property was insufficient is considered that the film thickness of the top coat film was too thin and the particle size of the gloss adjusting agent was too large relative to the film thickness T of the top coat film. .
  • the coated metal plate 19 was swollen by a volatile component during baking of the top coat film. Therefore, the evaluation test of the flat portion corrosion resistance could not be performed. This is considered because the film thickness of the top coat film was too thick.
  • the coated metal plates 20 and 21 were too glossy, and the desired design properties (enamel-like gloss) were not obtained.
  • the reason why the gloss of the coated metal plate 20 is too high is that the gloss coat is not contained in the top coat film, and the reason that the gloss of the coated metal plate 21 is too high is that the content of the gloss modifier is small. This is probably because the gloss was not adjusted sufficiently.
  • the coated metal plate 26 had a gloss that was too low, and the adhesion to the processed part was insufficient. Therefore, the evaluation test of the flat portion corrosion resistance could not be performed. This is considered because the content of the gloss adjusting agent in the top coat film was too much.
  • all of the coated metal plates 27 to 29 exhibit the desired design (enamel gloss) regardless of the type of the coated original plate (configuration of presence or absence of the undercoat film, etc.), work adhesion and flatness. It had sufficient corrosion resistance. This is thought to be because the flat portion corrosion resistance is provided by the top coat film.
  • coated metal plates 30 and 31 were more excellent in corrosion resistance on the flat portion than the coated metal plates 4 and 5 having the same configuration except that the coated metal plates 30 and 31 had a chromium-free coated original plate. This is presumably because the corrosion resistance was further enhanced by the rust prevention treatment by the chromate of the coating original plate.
  • both of the coated metal plates 32 and 33 exhibited the desired design (enamel gloss) regardless of the type of the gloss adjusting agent, and had sufficient work adhesion and flat portion corrosion resistance. This is considered to be because, even if the particles have pores, regardless of whether they are inorganic particles or organic particles, sufficient flat portion corrosion resistance is exhibited if they are not exposed from the surface of the top coat film.
  • the coated metal plate 34 showed excellent results in any evaluation. This is because the coated metal plate 34 has an intermediate coating film, so that the design and functionality of the intermediate coating film are imparted, and as a result, the design and functionality expressed only by the top coating film are better. This is thought to be due to the manifestation of various characteristics.
  • the coated metal plates 29, 30 and 31 all maintain the flat portion corrosion resistance for a longer period than the painted metal plate 4. This is because the coating original plate 4 in the coated metal plates 29, 30 and 31 contains a chromate rust preventive pigment in the undercoat coating film, and the chromate rust prevention treatment is applied to the plated steel plate. This is considered to be due to the high corrosion resistance over a long period of time as compared with the coating original plate 3 in the above.
  • the gloss modifier is particles up to 1.2 times (1.2 T) the film thickness of the top coat film, particles larger than 0.9 T are obtained. It can be seen that even if it is contained up to at least 2.5% by volume of particles of 0.9T or less, no substantial adverse effect is exerted on the flat portion corrosion resistance of the coated metal plate. This is because particles whose size is slightly larger than the film thickness T of the top coat film are likely to be arranged in a direction in which the major axis is along the direction of application of the top coat. This is thought to be because the resin continues to be sufficiently covered.
  • the gloss adjusting agent may contain a small amount of large particles (coarse particles) that are detected at positions deviating from the particle size distribution.
  • coarse particles are considered to be exposed from the top coat film during durable use and cause the corrosion resistance of the flat portion of the coated metal plate to be impaired.
  • an appropriate pulverization step is applied to the top coating material containing the coarse particles, a coated metal plate having sufficient flat portion corrosion resistance can be obtained. This is presumably because the coarse particles are pulverized small enough in the top coat to a degree sufficient for the coated metal plate to exhibit the desired flat portion corrosion resistance.
  • the coated metal plate according to the present invention prevents the corrosion resistance from being lowered at the flat portion due to the exposure, collapse and dropping of the gloss modifier from the top coat film. Therefore, even if it is used for a long period of time for exterior use, a coated metal plate that exhibits the desired appearance and corrosion resistance for a long period of time can be obtained. Therefore, the present invention is expected to further extend the life and further promote the use of the coated metal sheet for exterior use.
PCT/JP2014/006272 2014-08-12 2014-12-16 塗装金属板、その製造方法および外装建材 WO2016024305A1 (ja)

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RU2017107362A RU2665518C1 (ru) 2014-08-12 2014-12-16 Металлический лист с покрытием, способ его производства, а также наружный строительный материал
US15/503,161 US20170226645A1 (en) 2014-08-12 2014-12-16 Coated metal sheet, method for producing same, and exterior building material
EP14899841.2A EP3181352B1 (en) 2014-08-12 2014-12-16 An exterior building material and a method for producing same
KR1020177005085A KR102323367B1 (ko) 2014-08-12 2014-12-16 도장 금속판, 그 제조 방법 및 외장 건재
ES14899841T ES2779418T3 (es) 2014-08-12 2014-12-16 Un material de construcción para exteriores y un procedimiento de producción del mismo
CN201480082611.3A CN107073896B (zh) 2014-08-12 2014-12-16 外装建材及其制造方法

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JP5714753B1 (ja) * 2014-05-29 2015-05-07 日新製鋼株式会社 塗装金属板の製造方法および外装建材
JP5714756B1 (ja) * 2014-08-12 2015-05-07 日新製鋼株式会社 塗装金属板の製造方法および外装建材
JP6816608B2 (ja) * 2017-03-29 2021-01-20 日本製鉄株式会社 塗装金属板
JP7372541B2 (ja) 2020-02-12 2023-11-01 日本製鉄株式会社 化成処理鋼板
EP4144446A1 (en) * 2021-09-07 2023-03-08 TATA STEEL UK Limited Polymer coated sheet product and method of manufacturing it

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JP2007007562A (ja) * 2005-06-30 2007-01-18 Asahi Sunac Corp 多液塗料の供給装置及び方法

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TWI658107B (zh) 2019-05-01
TW201606003A (zh) 2016-02-16
EP3181352A4 (en) 2017-12-20
KR20170041766A (ko) 2017-04-17
EP3181352B1 (en) 2020-02-05
US20170226645A1 (en) 2017-08-10
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ES2779418T3 (es) 2020-08-17

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